Phthalocyanine compounds used in inks for ink jet printing

ABSTRACT

Suitable phthalocyanine compounds of Formula (1) have utility as colorants in inks for ink-jet printing, where Formula (1) represents:                    
     which comprises any form of the compound: such as salt; stereoisomer, zwitterion, polymorph, complex, isotopic form, combinations thereof in the same species and mixtures thereof; where: 
     M represents a metal or H; 
     Pc represents a phthalocyanine nucleus of Formula (2):                    
     L represents a linking group comprising an optionally substituted C 1-30 hydrocarbyl; 
     A represents a group comprising at least one of: amino and optionally substituted C 1-30 hydrocarbyl comprising at least one protonable nitrogen atom; but where A comprises other than an alkyl group substituted by at least one of: hydroxy, carboxy and sulpho; 
     R 1  represents a group independently comprising at least one of: an optional substituent and optionally substituted C 1-5 hydrocarbyl; 
     z represents an integer from 0 to 4; w represents an integer from 1 to 5; and the sum of w+z is from 1 to 5; and 
     x and y each independently represent a non-zero number; and the mean of the sum of x+y is from about 1 to about 6; 
     where the optional substituents comprise at least one of: carboxy, sulpho, hydroxy, amino, mercapto, cyano, nitro and halo.

This application is the national phase of international applicationPCT/GB98/02545 filed Aug. 24, 1998 which designated the U.S.

This invention relates to compounds, to ink compositions comprising themand to the use of such inks in ink jet printing (“IJP”). IJP is anon-impact printing technique in which droplets of ink are ejectedthrough a fine nozzle onto a substrate without bringing the nozzle intocontact with the substrate.

There are many demanding performance requirements for colorants and inksused in IJP. For example they desirably provide sharp, non-featheredimages having good water-fastness, light-fastness and optical density.The inks are often required to dry quickly when applied to a substrateto prevent smudging, but they should not form a crust over the tip of anink jet nozzle because this will stop the printer from working. The inksshould also be stable to storage over time without decomposing orforming a precipitate which could block the fine nozzle.

The compounds listed below are known from the prior art:

EP 0684292 discloses the following compounds (where Pc is aphthalocyanine nucleus as defined below):

Chemical Abstracts (CAS) 105038-63-9 discloses a compound of Formula I:

CAS 104994-17-4 discloses a compound of Formula II:

CAS 104994-15-4 discloses a compound of Formula III:

The preceding compounds are known per se but are not known for use ascolorants in IJP.

Surprisingly, the applicant has discovered that certain phthalocyaninecompounds have particular utility as colorants for use in IJP as theymay produce prints with unexpectedly good optical density, lightfastness and/or water fastness.

According to the present invention there is provided at least onecompound of Formula (1):

which comprises any form of the compound: such as salt; stereoisomer,zwitterion, polymorph, complex, isotopic form, combinations thereof inthe same species and mixtures thereof; where:

M represents a metal or H;

Pc represents a phthalocyanine nucleus of Formula (2):

L represents a linking group comprising an optionally substitutedC₁₋₃₀hydrocarbyl;

A represents a group comprising at least one of: amino and optionallysubstituted

C₁₋₃₀hydrocarbyl comprising at least one protonable nitrogen atom; butwhere A comprises other than an alkyl group substituted by at least oneof: hydroxy, carboxy and sulpho;

R¹ represents a group independently comprising at least one of: anoptional substituent and optionally substituted C₁₋₁₅hydrocarbyl;

z represents an integer from 0 to 4; w represents an integer from 1 to5; and the sum of w+z is from 1 to 5; and

x and y each independently represent a non-zero number; and the mean ofthe sum of x+y is from about 1 to about 6;

where the optional substituents comprise at least one of: carboxy,sulpho, hydroxy, amino, mercapto, cyano, nitro and halo;

with the provisos that:

when M is Cu; x and y are both 1.5; z is 0, w is 1 and L is p-SO₂C₂H₄then A is other than —NHCN; and

Formula (1) is other than a compound selected from: Formulae I, II andIII as defined herein and proton salts thereof.

The term “hydrocarbyl” as used herein denotes any radical moiety whichcomprises one or more hydrogen atoms with one or more carbon atoms andoptionally one or more other suitable heteroatoms, preferably nitrogen,oxygen and/or sulphur. More preferably the term ‘hydrocarbyl’ comprisesany of the following moieties and combinations thereof in the samemoiety: alkyl, alkoxy, alkanoyl, carboxy, alkanoyloxy, alkylthio,alkylsulphinyl, alkylsulphonyl, carbamoyl, sulphamoyl, alkylamino,and/or alkanoylamino. Hydrocarbyl moieties may also comprise one or moredouble and/or triple carbon to carbon bonds and/or aromatic moieties. Itwill be understood that the terms ‘alkyl’ or its equivalents (e.g.‘alk’) as used above may be readily replaced where appropriate by termsencompassing moieties comprising double bonds, triple bonds and/oraromatic moieties (e.g. alkenyl, alkynyl and/or aryl). The term ‘halo’as used herein signifies fluoro, chloro, bromo and iodo, preferablyfluro and chloro.

Any radical group mentioned herein as a substituent refers to amonovalent radical unless otherwise stated. A group which comprises achain of three or more atoms signifies a group in which the chain whollyor in part may be linear, branched and/or form a ring (including spiroand/or fused rings). The total number of certain atoms is specified forcertain substituents for example C_(1-n)hydrocarbyl, signifies anhydrocarbyl moiety comprising from 1 to n carbon atoms. In any of theformulae drawn herein if one or more ring substituents are not indicatedas attached to any particular atom on the ring [for example thesubstituent R¹ in Formula (1)] the substituent may replace any Hattached to an atom in the ring and may be located at any availableposition on the ring which is chemically suitable.

According to a further feature of the present invention there isprovided an ink suitable for use in IJP comprising a suitable medium anda colorant comprising a suitable compound of Formula (3):

which comprises any suitable form of the compound: such as salt;stereoisomer, zwitterion, polymorph, complex, isotopic form,combinations thereof in the same species and mixtures thereof; where:

M represents a suitable metal or H;

Pc represents a phthalocyanine nucleus of Formula (2) as defined herein;

L represents a suitable linking group comprising an optionallysubstituted C₁₋₃₀hydrocarbyl;

A represents a group comprising at least one of: amino and optionallysubstituted C₁₋₃₀hydrocarbyl comprising at least one protonable nitrogenatom; but where A comprises other than an alkyl group substituted by atleast one of: hydroxy, carboxy and sulpho;

R¹ represents a suitable group independently comprising at least one of:an optional substituent and optionally substituted C₁₋₁₅hydrocarbyl;

z represents an integer from 0 to 4; w represents an integer from 1 to5; and the sum of w+z is from 1 to 5; and

x and y each independently represent a non-zero number; and the mean ofthe sum of x+y is from about 1 to about 6;

where the optional substituents comprise at least one of: carboxy,sulpho, hydroxy, amino, mercapto, cyano, nitro and halo.

Preferably in the ink of the present invention the compounds of Formula(3) comprise dyes, more preferably dyes comprising a predominately cyancolour.

The terms ‘acceptable’ or ‘suitable’ (for example with reference tocomposition ingredients, substituents and/or compounds described herein)will be understood to mean suitable for use in IJP for example byproviding desirable properties to the ink or being compatible with anyinert carriers and/or diluents suitable for formulating such inks. Inrelation to the processes described herein suitable compounds are thosewhich will, in addition, undergo the specified reactions. To beparticularly acceptable for use in IJP compounds of Formulae (1) and (3)may be Ames negative.

In Formulae (1) and (3) when M is a metal it may be selected from anysuitable metal or mixtures thereof in the same complex. The metal mayexist in any suitable oxidation state and may be neutral or charged(i.e. an ion). The metal may also be bonded to one or more oxygen atoms.Preferred metals for M comprise Li, Na, K, Mg, Ca, Ba, Al, Si, Sn, Pb,Rh, Sc, Ti, V, Cr, Mn, Fe, Co, Ni and/or Cu, more preferably Sc, Ti, Va,Cr, Mn, Fe, Co, Zn, Ni and/or Cu and most preferably Ni and/or Cu.Especially preferred compounds of Formulae (1) and (3) are those inwhich M is Cu.

Preferred compounds of Formulae (1) and (3) are those in which: z is 0or 1; when z is 1, R¹ represents a group independently selected from:carboxy, carboxyC₁₋₆alkyl, sulpho, C₁₋₆alkyl, C₁₋₆alkoxy, halo, cyano,nitro, amino, C₁₋₆alkylamino di(C₁₋₆alkyl)amino, C₆₋₁₂arylamido (forexample benzamido) and C₁₋₆alkylsulphamoyl;

L represents a C₁₋₁₅hydrocarbyl group;

A represents an optionally substituted group selected from:

piperazinyl (optionally N-substituted by R²); —OR³; —SR³; and aminooptionally substituted by one or more R³; where:

R² comprises C₁₋₆alkyl optionally substituted by one or more amino (theamino being optionally N-substituted by one or more C₁₋₆alkyl); and

R³ comprises R² and/or —N(C₂H₂)₂Y; where Y represents NH, NR² or O;

w is 1 and;

x and y each represent from 1 to 3 and the sum of x+y is from 1 to 4.

More preferred compounds of Formulae (1) and (3) are those preferredcompounds in which

M is Cu;

L represents sulphonylC₁₋₁₅alkylene;

A comprises: piperazinylC₁₋₄alkylamino;N,N-diC₁₋₄alkylaminoC₁₋₄alkylamino; morpholinoC₁₋₄alkylamino; and/orpiperazinyl;

z is 0; and

x and y are both 2.

Specific compounds of Formulae (1) and (3) comprise those compoundsexemplified herein; any suitable salts thereof, preferably the ammoniumsalts; and any suitable mixtures thereof.

Compounds of Formulae (1) and (3) may be in the form as shown in thestructures herein (i.e. free acid form) but are preferably in the formof salts. Salts of Formulae (1) and (3) may be formed from one or moreorganic and/or inorganic bases and/or acids and compounds of Formulae(1) and (3) which are acidic and/or basic (for example acid and/or baseaddition salts). Salts of Formulae (1) and (3) comprise all acceptablesalts that may be formed from monovalent and/or multivalent acids and/orbases. Salts of Formulae (1) and (3) also comprise all enantiomericsalts formed with acceptable chiral acids and/or bases and/or anymixtures of enantiomers of such salts (for example racemic mixtures).Preferred salts are alkali metal salts, especially lithium, sodium andpotassium salts, ammonium and substituted ammonium salts. Especiallypreferred salts are salts with ammonia and volatile amines. The dyes maybe converted into a salt using known techniques. The present inventioncomprises all acceptable salts of Formulae (1) and (3) and any suitablemixtures thereof.

Certain compounds of Formulae (1) and (3) may exist as one or morestereoisomers, for example, enantiomers, diastereoisomers, geometricisomers, tautomers, conformers and/or suitable combinations thereofpossible in the same species. The present invention comprises allacceptable stereoisomers of compounds of Formulae (1) and (3) and anysuitable mixtures thereof.

Certain compounds of Formulae (1) and (3) may exist as one or morezwitterions, for example, species which comprise two or more centres ofionic charge. The present invention comprises all acceptable zwitterionsof Formulae (1) and (3) and any suitable mixtures thereof.

Certain compounds of Formulae (1) and (3) may exist as one or morepolymorphs, for example, phases, crystalline forms, amorphous forms,solid solutions, interstitial compounds and/or any suitable mixturesthereof. The present invention includes all acceptable polymorphs ofFormulae (1) and (3) and any suitable mixtures thereof.

Certain compounds of Formulae (1) and (3) may exist in the form of oneor more other complexes in addition to the metal complexes shown herein,for example, chelates, solvates, other organometallic complexes, and/orcomplexes with other suitable ligands. Such complexes may be formedbetween an acceptable substrate in which the compound of Formulae (1)and (3) and/or the substrate may act as a ligand. The substrate maycomprise one or more acceptable solvents to form solvates. The complexesmay be non-stoichiometric, for example if the complex is a hydrate itmay comprise a hemihydrate, monohydrate and/or dihydrate. The presentinvention includes all acceptable complexes of Formulae (1) and (3) andany suitable mixtures thereof.

Certain compounds of Formulae (1) and (3) may exist as one or moreisotopic forms in which one or more atoms in Formulae (1) and (3)comprise one or more suitable isotopes. The natural ratios of variousisotopes may be altered by suitable means, for example certain ¹²C atomsin certain compounds of Formulae (1) and (3) may be substantiallyreplaced by the less common ¹⁴C and/or ¹³C isotopes. Optionally certainisotopic forms of Formulae (1) and (3) may be radio-active. Certain ofthe isotopic forms of Formulae (1) and (3) may be used as means forselective imaging in imaging devices (for example devices using X-rays,positron emission tomography and/or nuclear magnetic resonance); and/oras tools to investigate the mode of action of compounds of Formulae (1)and (3) in IJP. The present invention includes all acceptable, isotopicforms of Formulae (1) and (3) and any suitable mixtures thereof.

The present invention relates to all compounds of Formula (1) even thosewhich may not be directly acceptable for use in IJP because they exhibitundesirable properties. Such compounds may nevertheless have utility inthe field of the present invention for example as intermediates in thepreparation and/or purification of acceptable compounds of Formulae (1)and (3) and/or as research tools and/or diagnostic aids in relation toIJP.

Compounds of Formulae (1) and (3) may be prepared the methods describedbelow and by other suitable methods analogous to those described in theart for similar phthalocyanine compounds.

A preferred method for preparing compounds of Formulae (1) and (3) inwhich L is SO₂C₂H₄ comprises reacting compounds of Formula (4):

with compounds of formula AH where Pc, R¹ and A are as defined above.Compounds of Formula (4) in which M is Cu, z is 0 and w is 1 areavailable commercially.

The reactions leading to the formation of the present compounds may beperformed under conditions that have been described in the art andcompounds of Formulae (1) and (3) may be isolated by known methods suchas spray drying or precipitation followed by filtration.

Preferably the ink of the present invention comprises:

(a) from 0.01 to 30 parts of the compound of the Formula (3); and

(b) from 70 to 99.99 parts of a liquid medium or a low melting pointsolid medium; wherein all parts are by weight and the number of parts of(a)+(b)=100.

The number of parts of component (a) is preferably from 0.1 to 20, morepreferably from 0.5 to 15, and especially from 1 to 5 parts. The numberof parts of component (b) is preferably from 99.9 to 80, more preferablyfrom 99.5 to 85, especially from 99 to 95 parts.

When the medium is a liquid, preferably component (a) is completelydissolved in component (b). Preferably component (a) has a solubility incomponent (b) at 20° C. of at least 10%. This allows the preparation ofconcentrates which may be used to prepare more dilute inks and reducesthe chance of the colorant precipitating if evaporation of the liquidmedium occurs during storage.

Preferred liquid media include water, a mixture of water and an organicsolvent and an organic solvent free from water.

When the medium comprises a mixture of water and an organic solvent, theweight ratio of water to organic solvent is preferably from 99:1 to1:99, more preferably from 99:1 to 50:50 and especially from 95:5 to80:20. Preferably the organic solvent comprising the mixture of waterand organic solvent is a water-miscible organic solvent or a mixture ofsuch solvents. The liquid medium may comprise water and preferably twoor more, more preferably from 2 to 8, water-soluble organic solvents.

Preferred water-miscible organic solvents comprise:

C₁₋₆alkanols, preferably methanol, ethanol, n-propanol, isopropanol,n-butanol, sec-butanol, tert-butanol, n-pentanol, cyclopentanol and/orcyclohexanol;

linear amides, preferably dimethylformamide and/or dimethylacetamide;ketones and/or ketone-alcohols, preferably acetone, methyl ether ketone,cyclohexanone and/or diacetone alcohol;

water-miscible ethers, preferably tetrahydrofuran and/or dioxane;

diols, preferably C₂₋₁₂diols (for example pentane-1,5-diol, ethyleneglycol, propylene glycol, butylene glycol, pentylene glycol, hexyleneglycol and/or thiodiglycol) and/or oligo- and/or poly-alkyleneglycols(for example diethylene glycol, triethylene glycol, polyethylene glycoland/or polypropylene glycol);

triols, preferably glycerol and/or 1,2,6-hexanetriol;

C₁₋₄alkyl ethers of diols, preferably monoC₁₋₄alkyl ethers ofC₂₋₁₂diols: {for example 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol,2-(2-ethoxyethoxy)-ethanol, 2-[2-(2-methoxyethoxy)ethoxy]-ethanol,2-[2-(2-ethoxyethoxy)-ethoxy]-ethanol and/or ethyleneglycol monoallylether};

cyclic amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone,N-ethyl-2-pyrrolidone, caprolactam and/or 1,3-dimethylimidazolidone;

cyclic esters, preferably caprolactone;

sulphoxides, preferably dimethyl sulphoxide and/or sulpholane; and/orany suitable mixtures thereof.

More preferred water-soluble organic solvents are selected from: cyclicamides (e.g. 2-pyrrolidone, N-methyl-pyrrolidone andN-ethyl-pyrrolidone);

diols, (e.g. 1,5-pentane diol, ethyleneglycol, thiodiglycol,diethyleneglycol and triethyleneglycol);

C₁₋₄alkyl ethers of diols (e.g. 2-methoxy-2-ethoxy-2-ethoxyethanol); and

any suitable mixtures thereof.

A preferred liquid medium comprises:

(a) from 75 to 95 parts water; and

(b) from 25 to 5 parts in total of one or more solvents selected from:

diethylene glycol, 2-pyrrolidone, thiodiglycol, N-methylpyrrolidone,cyclohexanol, caprolactone, caprolactam and pentane-1,5-diol;

where the parts are by weight and the sum of the parts (a)+(b)=100.

Another preferred liquid medium comprises:

(a) from 60 to 80 parts water;

(b) from 2 to 20 parts diethylene glycol; and

(c) from 0.5 to 20 parts in total of one or more solvents selected from:

2-pyrrolidone, N-methylpyrrolidone, cyclohexanol, caprolactone,caprolactam, pentane-1,5-diol and thiodiglycol;

where the parts are by weight and the sum of the parts (a)+(b)+(c)=100.

Examples of further suitable media for inks of the present inventioncomprise a mixture of water and one or more organic solvents aredescribed in U.S. Pat. No. 4,963,189, U.S. Pat. No. 4,703,113, U.S. Pat.No. 4,626,284 and EP 0425150-A.

When the liquid medium comprises an organic solvent free from water,(i.e. less than 1% water by weight) the solvent preferably has a boilingpoint of from 300 to 200° C., more preferably of from 400 to 150° C.,especially from 50 to 125° C. The organic solvent may bewater-immiscible, water-miscible or a mixture of such solvents.Preferred water-miscible organic solvents comprise any of thosedescribed above and mixtures thereof. Preferred water-immisciblesolvents comprise aliphatic hydrocarbons; esters (for example ethylacetate) chlorinated hydrocarbons (for example dichloromethane), ethers(for example diethyl ether) and mixtures thereof.

When the liquid medium comprises a water-immiscible organic solvent,preferably it comprises a polar solvent (for example a C₁₋₄alkanol) toenhance the solubility of the dye in the liquid medium. It is especiallypreferred that where the liquid medium is an organic solvent free fromwater it comprises a ketone (especially methyl ethyl ketone) and/or analcohol (especially a C₁₋₄alkanol, more especially ethanol or propanol).

The organic solvent free from water may be a single organic solvent or amixture of two or more organic solvents. It is preferred that when themedium is an organic solvent free from water it is a mixture of 2 to 5different organic solvents. This allows a medium to be selected whichgives good control over the drying characteristics and storage stabilityof the ink.

Ink media comprising an organic solvent free from water are particularlyuseful where fast drying times are required and particularly whenprinting onto hydrophobic and non-absorbent substrates, for exampleplastics, metal and glass.

Preferred low melting solid media have a melting point in the range from60° C. to 125° C. Suitable low melting point solids include long chainfatty acids or alcohols, preferably those with C₁₈₋₂₄chains, andsulphonamides. The dye of Formula (3) may be dissolved in the lowmelting point solid or may be finely dispersed in it.

The ink may also contain additional components conventionally used ininks for IJP, for example viscosity and surface tension modifiers,corrosion inhibitors, biocides, kogation reducing additives andsurfactants which may be ionic or non-ionic.

A further aspect of the invention provides a process for printing animage on a substrate comprising applying to the substrate by means of anink jet printer, an ink of the present invention as defined herein.

The ink jet printer preferably applies the ink to the substrate in theform of droplets which are ejected through a small orifice onto thesubstrate. Preferred ink jet printers are piezoelectric ink jet printersand thermal ink jet printers. In thermal ink jet printers, programmedpulses of heat are applied to the ink in a reservoir by means of aresistor adjacent to the orifice, thereby causing the ink to be ejectedin the form of small droplets directed towards the substrate duringrelative movement between the substrate and the orifice. Inpiezoelectric ink jet printers the oscillation of a small crystal causesejection of the ink from the orifice.

The substrate is preferably paper, plastic, a textile, metal or glass,more preferably paper, an overhead projector slide or a textilematerial, especially paper. Preferred papers are plain or treated paperswhich may have an acid, alkaline or neutral character.

A further aspect of the present invention provides a paper, an overheadprojector slide or a textile material printed with an ink and/or acolorant as defined herein and/or by means of a process as definedherein.

When the substrate is a textile material the ink according to theinvention is preferably applied thereto by:

i) applying the ink to the textile material using an ink jet printer;and

ii) heating the printed textile material at a suitable temperature,preferably from 50° C. to 250° C., to fix the ink on the material.

Preferred textile materials are natural, synthetic and semi-syntheticmaterials. Examples of preferred natural textile materials include wool,silk, hair and cellulosic materials, particularly cotton, jute, hemp,flax and linen. Examples of preferred synthetic and semi-syntheticmaterials include polyamides, polyesters, polyacrylonitriles andpolyurethanes.

Preferably the textile material has been treated with an aqueouspre-treatment composition comprising a thickening agent and optionally awater-soluble base and a hydrotropic agent and dried prior to step i)above.

The pre-treatment composition preferably comprises a solution of thebase and the hydrotropic agent in water containing the thickening agent.Particularly preferred pre-treatment compositions are described morefully in EP 0534660-A.

The invention is further illustrated by the following Examples in whichall parts and percentages are by weight unless otherwise stated.

EXAMPLE 1

Preparation of

a) Preparation of

CuPC(SO₂Cl)₄

Copper phthalocyanine (115 g) was added in portions to stirredchlorosulphonic acid (310 ml) over 30 minutes keeping the temperaturebelow 50° C. The mixture was stirred for 30 minutes at 50° C. beforebeing heated gradually to 135-140° C. over one hour. The temperature ofthe mixture was maintained at 140° C. and it was stirred for 3 hours andthen cooled to room temperature.

The mixture was heated to 45° C. and phosphorus trichloride (52.3 g) wasadded dropwise over 1 hour 15 minutes, whilst the temperature was keptat 45-50° C. The temperature of the mixture was raised to 90° C. and wasmaintained at this for 3 hours and then cooled to room temperature.

The resulting solution was poured onto a stirred mixture of ice (1 kg),water (200 ml), concentrated hydrochloric acid (44 ml) and sodiumchloride (40 g) maintained at a temperature of 0° C. The precipitatedproduct was collected by filtration at reduced pressure and washed withice-cold hydrochloric acid solution (0.5 M, 2 l) to obtain a paste whichwas dried under reduced pressure to obtain CuPc(SO₂Cl)₄ which was useddirectly in the next step

b) Preparation of

The sulphonyl chloride from step a) was added to a mixture ofp-aminobenzenesulphatoethylsulphone (112.4 g) in water (500 ml) and ice(500 g). The mixture was stirred for 10-15 minutes and then the pH ofthe mixture was raised to 6.5-7.0 with caustic liquor. The mixture wasstirred at room temperature for 18 hours whilst maintaining the pH at7.0 by adding 2N NaOH. Sodium chloride (10% w/v) was added to themixture which was stirred for 20 minutes and the pH of the mixture wasadjusted to 2.5 with concentrated hydrochloric acid. The mixture wasstirred for a further 30 minutes and the resultant precipitate wascollected by filtration at reduced pressure and washed with ice coldbrine (10%) and dried under reduced pressure to obtain 954.8 g ofproduct.

c) Preparation of title compound.

The compound from step b) above (318 9) was stirred in distilled water(700 g) and the pH of the solution was adjusted to 6.5-7.0 with 2N NaOH.1-(2-Aminoethyl)piperazine (34.05 g) was added to this solution and themixture was heated to 80-85° C. and maintained at this temperature for18 hours.

The mixture was cooled to room temperature and sodium chloride (20% w/v)was added and the pH of the mixture was adjusted to 7.0 withconcentrated hydrochloric acid. The mixture was stirred and cooled to10° C. and stirred at this temperature for a further 30 minutes. Theresultant precipitate was collected by filtration at reduced pressureand washed with brine (20%) to obtain a paste which was dried at reducedpressure in an oven to given the title compound.

EXAMPLE 2

Preparation

This compound was prepared as described in Example 1 substitutingN,N-dimethylethylenediamine (23.18 g) for the 1-(2-aminoethyl)piperazineused in step 1c.

EXAMPLE 3

Preparation of

This compound was prepared as described in Example 1 substituting4-(3-aminopropyl)morpholine (37.93 g) for the 1-(2-aminoethyl)piperazineused in step 1c.

EXAMPLE 4

Preparation of

This compound was prepared as described in Example 1 substitutingpiperazine (22.65 g) for the 1-(2-aminoethyl)piperazine used in step 1c.

EXAMPLE 5

(S 171165)

Preparation of

This compound was prepared as described in Example 1 substituting1,4-bis(3-aminopropyl)piperazine (52.68 g) for the1-(2-aminoethyl)piperazine used in step 1c.

Salts

The exemplified compounds 1 to 5, prepared as described above, wereconverted to their purified ammonium salts as follows. Each example wasdissolved in distilled water. The solution was filtered and the volumeof the filtrate adjusted to 4 l. The solution was desalinated by reverseosmosis. The dissolved sodium salt was converted into the ammonium saltby passing the solution through an ion-exchange column comprising DowexHGRW resin staturated with ammonia. The solution of the ammonium saltthus obtained was then filtered and water was evaporated form thefiltrate to yield a purified ammonium salt suitable for use directly inan ink as described below.

Inks

The effectiveness in ink jet printing of compounds of Formula (1) wasdemonstrated as follows. Inks separately comprising each exemplified dyewere prepared by dissolving 2 parts of the ammonium salt, prepared asdescribed above, in 98 parts of a mixture of water and 2-pyrrolidone (ina respective ratio of 90:10 by volume). The inks were printed onto plainpaper using a thermal ink-jet printer to give a bright cyan prints whichhad good optical density and excellent water and light fastness.

Further inks comprising the exemplified dyes may be may be prepared asdescribed in the following tables in which the number in the firstcolumn (headed Ex. no.) denotes the example number of dye to be used inthe ink. The dye may be in its free acid form and/or in the form of anysuitable salt (e.g. ammonium salt). Numbers quoted in the second columnonwards refer to the number of parts of the relevant ingredient and allparts are by weight. The inks may be applied to paper by thermal orpiezo ink jet printing.

The following abbreviations are used in the tables:

PG = propylene glycol; DEG = diethylene glycol; NMP = N-methylpyrollidone; DMK = dimethylketone; NaST = Na stearate IPA = isopropanol;MEOH = methanol; 2P = 2-pyrollidone; MIBK = methylisobutyl ketone; CET =cetyl ammonium bromide; TBT = tertiary butanol; TDG = thiodiglycol; BDL= butane-2,3-diol; PHO = Na₂HPO₄; P12 = propane-1,2-diol. CHL =cyclohexanol; and PDL = pentan-1,5-diol.

TABLE I Ex. no. Dye Water PG DEG NMP DMK MEOH 2P MIBK 1 2.0 80 5 6 4 5 210.0 85 3 3 3 5 1 3 2.1 91 8 1 4 2.4 75 3 4 5 6 5 5 5.1 96 4 1 1.8 80 515 2 2.6 84 11 5 3 3.3 80 2 10 2 6 4 5.4 69 2 20 2 1 3 3 5 7.0 70 15 310

TABLE II Ex. No. Dye Water PG DEG NMP NaOH Na ST IPA 2P MIBK 1 2.0 70 76 3 2 2 4.0 65 4 6 0.7 5 3 1.0 50 4 5 1 4 3.1 86 5 2 0.2 4 5 5 1.1 81 29 0.5 0.5 9

TABLE III Ex. no. Dye Water PG DEG NMP DMK IPA MEOH 2P MIBK 1 3.1 86 5 45 2 1.1 81 9 9 3 2.5 60 4 15 3 3 6 10 5 4 4 3.2 65 5 4 6 5 4 6 5 5 10.080 2 6 2 5 1 4

TABLE IV Ex. no. Dye Water PG DEG NMP DMK NaOH Na ST IPA 1 3.0 90 5 50.2 2 5 65 5 20 10 3 4.1 80 5 2 10 0.3 4 10.8 90 5 5 5 12.0 90 7 0.3 3

TABLE V Ex. no. Dye Water PG DEG NMP CET PHO 2P P12 1 3.0 80 15 0.2 5 29.0 90 5 1.2 5 3 2.5 90 6 4 0.12 4 3.1 82 4 8 0.3 6 5 10.0 91 6 3 1 5.078 5 11 6 2 6.0 63 3 4 2.0 3 3.0 72 15 0.8 3 4 5.4 86 5 7 3.0 7 5 2.0 9010 10

TABLE VI Ex. no. Dye Water PG DEG NMP CET TBT TDG 1 1.5 85 5 5 0.15 5.00.2 2 9.0 90 5 5 0.3 3 2.0 90 10 4 2.0 88 10 5 5.5 70 4 4 0.4 3

TABLE VII Ex. no. Dye Water PG DEG NMP TBT TDG BDL PHO 2P 1 0.9 85 10 50.2 2 4.0 70 10 4 1 4 3 2.2 75 4 10 3 2 6 4 9.0 76 9 7 3.0 0.95 5 5 2.170 5 5 5 0.2 0.1 5 0.1 5

TABLE VIII Ex. no. Dye Water PG DEG NMP TBT TDG 2P 1 3.0 55 5 2.0 3 26.0 65 4 0.1 5 3 5.0 78 5 12 5 4 8.0 70 2 8 15 5 5 10.0 80 8 12

TABLE IX Ex. no. Dye Water PG DEG NMP BDL PHO 2P P12 1 10.0 75 3 5 3 3 12 3.5 80 6 5 3 2.0 90 7 7 0.5 4 6.0 65 5 2 5 4.0 70 10 4 1 4 11

TABLE X Ex. no. Dye Water PG DEG NMP CET TBT TDG BDL PHO 2P 1 1.5 80 1 23 0.5 0.4 7 2 10 2 3.0 60 4 2.0 0.5 3 4.5 90 3 6 7.0 1 3 2 4 3.0 95 7 43 0.5 5 2.1 70 5 5 5 0.1 0.2 0.1 5 0.1 5

TABLE XI Ex. no. Dye Water PG DEG NMP CHL PHO 2P PDL 1 7.0 75 3 5 3 3 12 3.5 60 2 5 3 2.0 90 7 7 1.5 2 4 6.0 65 5 2 5 4.0 70 5 4 1 4 12

What is claimed is:
 1. At least one compound of Formula (1):

which comprises any form of the compound; where: M represents a metal orH; Pc represents a phthalocyanine nucleus of Formula (2):

L represents sulphonylC₁₋₁₅alkylene; A representspiperazinylC₁₋₄alkylamino; N,N-diC₁₋₄alkylaminoC₁₋₄alkylamino;morpholinoC₁₋₄alkylamino: and/or piperazinyl; R¹ represents a groupindependently comprising at least one of: an optional substituent andoptionally substituted C₁₋₁₅hydrocarbyl; z represents an integer from 0to 4; w represents an integer from 1 to 5; and the sum of w+z is from 1to 5; and x and y each independently represent a non-zero number; andthe mean of the sum of x+y is from about 1 to about 6; and where theoptional substituents comprise at least one of: carboxy, sulpho,hydroxy, amino, mercapto, cyano, nitro and halo.
 2. A compound accordingto claim 1 wherein M is Ni and/or Cu.
 3. A compound according to claim 1wherein M is Cu; L represents sulphonylC₁₋₁₅alkylene; A comprises:piperazinylC₁₋₄alkylamino; N,N-diC₁₋₄alkylaminoC₁₋₄alkylamino;morpholinoC₁₋₄alkylamino; and/or piperazinyl; z is 0; and x and y areboth
 2. 4. A compound according to claim 1 in the form of a salt.
 5. Acompound according to claim 4 wherein the salt comprises an alkali metalsalt.
 6. A compound according to claim 4 wherein the salt comprises asalt with ammonia or a volatile amine.
 7. An ink suitable for use in inkjet printing, comprising a suitable medium and a colorant comprising asuitable compound of Formula (3):

which comprises any form of the compound where: M represents Ni or Cu;Pc represents a phthalocyanine nucleus of Formula (2) as defined inclaim 1; L represents sulphonylC₁₋₁₅alkylene; A representspiperazinylC₁₋₄alkylamino; N,N-diC₁₋₄alkylaminoC₁₋₄alkylamino;morpholinoC₁₋₄alkylamino; and/or piperazinyl; R¹ represents a groupindependently comprising at least one of: an optional substituent andoptionally substituted C₁₋₁₅hydrocarbyl; z represents an integer from 0to 4; w represents an integer from 1 to 5; and the sum of w+z is from 1to 5; and x and y each independently represent a non-zero number; andthe mean of the sum of x+y is from about 1 to about 6; where theoptional substituents comprise at least one of: carboxy, sulpho,hydroxy, amino, mercapto, cyano, nitro and halo.
 8. A process forprinting an image on a substrate comprising applying to the substrate bymeans of an ink-jet printer an ink as described in claim
 7. 9. Asubstrate printed by a process as claimed in claim 8, the substrateselected from the group consisting of one or more of: paper, an overheadprojector slide and a textile material.
 10. A process for the colouringa textile material with an ink as claimed in claim 7, the processcomprising the steps of. i) applying the ink to the textile material byink-jet printing; and ii) heating the textile material at 50° C. to 250°C. to fix the ink on the material.
 11. A textile material coloured withany ink as claimed in claim
 7. 12. An ink according to claim 7 whereinthe fluid medium comprises water or a mixture of water and an organicsolvent.
 13. An ink according to claim 7 wherein the fluid mediumcomprises water and a water-miscible organic solvent or a mixture ofsuch solvents.
 14. An ink according to claim 7 wherein the fluid mediumcomprises an organic solvent free from water.